JP2013218288A - Toner for electrostatic charge image development, developer using the same, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that uses a crystalline resin, can suppress contamination due to attachment of a mold release agent to a paper ejection member after fixing, and has excellent releasability in fixing especially to thin paper.SOLUTION: (1) A toner including at least a binder resin and a mold release agent, wherein the binder resin includes a resin having a crystalline polyester unit as a main component, and the mold release agent contains 40 mass% or more of linear monoester having 48 or more carbon atoms. (2) A toner according to (1), wherein the resin having a crystalline polyester unit has either one of a urethane bond and a urea bond. (3) A toner according to (1) or (2), wherein the resin having a crystalline polyester unit is a block polymer of polyester and polyurethane.

Description

  The present invention relates to an electrostatic charge image developing toner, a developer using the toner, and an image forming apparatus.

In recent years, printers and MFPs (multifunction peripherals) that use electrophotographic image forming apparatuses have been required to be environmentally friendly. For example, CO ₂ emissions can be reduced by reducing the power consumed by printers and MFPs. Attempts have been made to make it closer to carbon neutral by using biomass material as a raw material. Under such a background, it is desired to lower the fixing temperature as an electrophotographic toner. For example, as a binder resin used in toner, a typical example is a crystalline polyester that melts instantaneously by heating during fixing. It is already known to add crystalline resins to be added. In addition, a method using a crystalline resin as a main component as a binder resin is already known (Patent Documents 1 and 2).

In general, the toner contains a release agent such as wax in order to impart releasability from the fixing member at the time of fixing. A release agent is also required in toners using a crystalline polyester resin as a main component. For example, hydrocarbon waxes such as paraffin wax and microcrystalline wax are often used as mold release agents, but if these waxes are used, deposits will be laminated on the paper discharge member after fixing, and the fixed image will be displayed. Damaged image quality could be damaged. On the other hand, if an ester wax having an ester bond site in the molecule is used as a mold release agent, the deposits on the paper discharge member will not be noticeable, but the mold release performance will not be fully exhibited, and especially thin paper When the upper image is fixed, paper wrapping may occur.
As a technique similar to the present invention, Patent Document 3 discloses the use of crystalline fine particles having specific storage elastic modulus and loss elastic modulus as resin particles excellent in low-temperature fixability and blocking resistance. Furthermore, although it is described that fatty acid esters such as behenyl behenate can be used as a release agent, there is a problem that the paper discharge member after the fixing is contaminated, particularly, the fixing releasability to thin paper is low.

  An object of the present invention is to provide a toner that can suppress contamination due to adhesion of a release agent to a discharged paper discharge member after fixing in a toner using a crystalline resin, and is particularly excellent in fixing releasability for thin paper.

As a result of intensive studies by the present inventors, the content of the linear monoester having 48 or more carbon atoms in the release agent is 40% by mass or more, so that even when fixing an image on thin paper, As a result, it was found that contamination due to adhesion of the release agent to the paper discharge member can be suppressed, and the present invention has been achieved.
That is, the above problem is solved by the following invention 1).
1) In a toner containing at least a binder resin and a release agent, and the main component of the binder resin is a resin having a crystalline polyester unit, the release agent contains a linear monoester having 48 or more carbon atoms. A toner having an amount of 40% by mass or more.

  According to the present invention, in a toner using a crystalline resin, contamination due to adhesion of a release agent to a paper discharge member after fixing can be suppressed, and a toner excellent in fixing releasability particularly for thin paper can be provided.

The figure which shows an example of the diffraction spectrum obtained by X-ray-diffraction measurement. The figure which shows the other example of the diffraction spectrum obtained by X-ray-diffraction measurement. Explanatory drawing of the solid image used by fixing releasability evaluation.

Hereinafter, the present invention 1) will be described in detail. In addition, since the following 2) -15) is also included in embodiment of this invention, these are also demonstrated collectively.
2) The toner according to 1), wherein the releasing agent has a melting point of 80 ° C. or lower.
3) The toner according to 1) or 2), wherein an endothermic peak half-value width of the release agent is 10 ° C. or less.
4) The toner according to any one of 1) to 3), wherein the content of the releasing agent is 3 to 20% by mass.
5) In the diffraction spectrum obtained by the X-ray diffractometer of the toner, (C) represents the integrated intensity of the spectrum derived from the crystal structure of the binder resin, and (A) represents the integrated intensity of the spectrum derived from the amorphous structure. The toner according to any one of 1) to 4), wherein the ratio (C) / [(C) + (A)] is 0.15 or more.
6) The maximum endothermic peak T1 at the second temperature increase in the range of 0 to 150 ° C. in the DSC of the toner and the maximum exothermic peak T2 at the time of temperature decrease satisfy the following relational expression (1): The toner according to any one of 5).
T1-T2 ≦ 30 ° C. and T2 ≧ 30 ° C. (1)
(However, the rate of temperature increase from 0 ° C. to 100 ° C. at the time of temperature increase is 10 ° C./min, and the rate of temperature decrease from 100 ° C. to 0 ° C. is 10 ° C./min.)
7) The ratio of the molecular weight of 100,000 or more in gel diffusion chromatography (GPC) measurement of tetrahydrofuran (THF) soluble content of the toner is 5% by mass or more, and the weight average molecular weight (Mw) is 20,000 to The toner according to any one of 1) to 6), which is 70,000.
8) The differential scanning calorimeter (DSC) of the toner has an endothermic amount of ΔH (T) (J / g), and the differential scanning of the insoluble content of the toner with respect to the THF / ethyl acetate mixed solvent (50/50 by weight). ΔH (H) / ΔH (T) is 0.2 to 1.25 when the endothermic amount in the calorimeter (DSC) is ΔH (H) (J / g) 1) to 7 The toner according to any one of the above.
9) The toner according to any one of 1) to 8), wherein the resin having a crystalline polyester unit has either a urethane bond or a urea bond.
10) The toner according to any one of 1) to 9), wherein the resin having a crystalline polyester unit is a block polymer of polyester and polyurethane.
11) The toner according to any one of 1) to 10), which contains two or more kinds of resins having the crystalline polyester unit.
12) The toner according to any one of 1) to 11), which is obtained by granulation in an aqueous medium.
13) Among the above resins, at least one is a modified crystalline resin having an isocyanate group at the terminal, and when the toner particles are granulated by dispersing or emulsifying in an aqueous medium, by reaction with active hydrogen groups. The toner according to any one of 1) to 12), wherein the binder resin is formed by elongation or crosslinking reaction.
14) A developer comprising the toner according to any one of 1) to 13) and a carrier.
15) an electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, exposure means for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, Developing means for developing the electrostatic latent image with toner to form a visible image, transfer means for transferring the visible image to a recording medium, and fixing for fixing the transferred image transferred to the recording medium An image forming apparatus having at least means, wherein the toner is the toner according to any one of 1) to 13).

The effects of the present invention are considered to be manifested for the following reasons.
The resin having a crystalline polyester unit used as the main component of the binder resin in the present invention has more alkylene sites than the non-crystalline polyester resin often used conventionally. Therefore, if the proportion of the linear monoester having less than 48 carbon atoms in the release agent is large, the affinity with the resin having a crystalline polyester unit increases, and a part of the resin and the release agent are mixed. Therefore, the mold release performance is lowered as compared with the case where the conventional amorphous polyester resin is the main component. In particular, when fixing an image on thin paper, it is considered that the releasability is insufficient due to the weakness of the paper, and winding around the fixing member occurs. That is, when the main component of the binder resin is a resin having a crystalline polyester unit with many alkylene sites, a release agent such as a wax having an alkyl chain and an ester bond is not low in polarity because of a large number of carbon atoms. And sufficient releasability cannot be demonstrated.
However, as in the present invention, if the content of the linear monoester having 48 or more carbon atoms in the release agent is 40% by mass or more, the paper can be wound even when fixing an image on thin paper. It can be suppressed. Further, even if the number of carbon atoms is 48 or more, a compound having two or more ester sites has insufficient release performance because of a large number of polar sites. Therefore, monoester is used in the present invention.

  Contamination due to the release agent adhering to the paper discharge member can be seen in paraffin wax and microcrystalline wax with low polarity, but these waxes volatilize in a small amount during fixing and are cooled by the paper discharge member. It is thought that it adhered. In order to suppress the volatility, a method of increasing the molecular weight of the release agent can be considered, but if a hydrocarbon wax such as polyethylene or polypropylene is used, the adhesion to the paper discharge member can be suppressed, but the wax itself Since the melting point is high, in the toner mainly composed of a resin having a crystalline polyester unit as in the present invention, the wax does not melt at the time of fixing and the releasing function is not exhibited. On the other hand, it is considered that the ester wax having an ester bond site in the molecule is less likely to volatilize due to the cohesive energy of the ester bond site, and contamination of the paper discharge member is suppressed.

<Release agent>
In the present invention, a release agent having a linear monoester content of 48 or more carbon atoms of 40% by mass or more is used. If the carbon chain has a branched structure, the compatibility with the binder resin is increased, and the fixing release effect is reduced. Therefore, it is necessary to use a linear monoester.
The content of the linear monoester is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 95% by mass or more. The higher the content, the better the fixing releasability, and the less the contamination due to the release agent adhering to the paper discharge port.
Examples of the linear monoester used in the present invention include synthetic ester compounds and natural ester waxes.

The synthetic ester compound is obtained by an esterification reaction from a linear higher alcohol and a linear higher carboxylic acid or a linear higher carboxylic acid halide.
Examples of the linear higher alcohol include stearyl alcohol, aralkyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol, and triacontanol. Examples of the linear higher carboxylic acid include Examples thereof include stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid and the like.

  As a method for producing a synthetic ester compound, for example, an esterification reaction (condensation reaction) is first performed using the above linear higher carboxylic acid in excess with respect to the above linear higher alcohol component, and an excess of the linear higher alcohol component is obtained. The method of removing carboxylic acid by deoxidation using aqueous alkali solution is mentioned. In this reaction, a catalyst may be used as necessary. In addition, since the esterification reaction is an equilibrium reaction accompanied by dehydration, the esterification reaction may be performed while distilling off water in the system. The reaction is carried out at such a high temperature that water in the system can be distilled off and reaction raw materials do not escape from the system.

Natural ester wax is obtained by separating and purifying wax collected from animals and plants.
Examples thereof include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, beeswax, lanolin wax, montan wax, sunflower wax and the like. However, since natural ester wax is a mixture composed of many kinds of compounds, it is necessary to separate and purify the release agent used in the present invention in some cases. Among these, sunflower wax is preferable because it contains a large amount of linear monoester having a large number of carbon atoms.

65-80 degreeC is preferable and, as for melting | fusing point of the mold release agent used by this invention, More preferably, it is 70-80 degreeC. If the temperature is lower than 65 ° C., the heat-resistant storage stability of the toner may be deteriorated. On the other hand, if the temperature exceeds 80 ° C., it is difficult to melt at the time of fixing, and the release performance may not be sufficiently exhibited. Further, the half-value width of the endothermic peak of the release agent is preferably 10 ° C. or less, and more preferably 8 ° C. or less. When the temperature exceeds 10 ° C., there are many components that melt at low temperatures and components that do not melt at high temperatures. Therefore, components that melt at low temperatures may adversely affect the heat-resistant storage stability of the toner. There is a possibility that a component that does not contribute to fixing releasability.
The content of the release agent in the toner is preferably 3 to 20% by mass, more preferably 4 to 14% by mass. If it is less than 3% by mass, the release performance at the time of fixing is difficult to be exhibited, and if it exceeds 20% by mass, the heat-resistant storage stability may be deteriorated and contamination due to adhesion of the release agent to the paper discharge port may be seen.

<Binder resin>
The binder resin used in the present invention is mainly composed of a resin having a crystalline polyester unit. Specifically, the resin having a crystalline polyester unit is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass, and still more preferably 90% by mass or more of the entire binder resin. This is because the more the resin having a crystalline polyester unit, the better the low-temperature fixability of the toner.
The resin having a crystalline polyester unit includes a resin composed only of a crystalline polyester unit (also simply referred to as a crystalline polyester resin), a resin in which a crystalline polyester unit is linked, and a crystalline polyester unit and another polymer bonded together. Resin (so-called block polymer, graft polymer). Resins consisting only of crystalline polyester units have a high degree of crystallinity, but from the viewpoint of imparting toughness to the resin, the crystallinity has ester bond sites, urethane bond sites, urea bond sites, and phenylene sites with high cohesive energy. A resin in which a polyester unit is connected and a resin in which a crystalline polyester unit and another polymer are bonded (so-called block polymer or graft polymer) are preferable.

<Crystalline polyester unit>
Examples of the crystalline polyester unit include a polycondensation polyester unit synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid. Among these, a polycondensation polyester unit of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity.

-Polyol-
Examples of the polyol include diols, trivalent to octavalent or higher polyols.
There is no restriction | limiting in particular as said diol, According to the objective, it can select suitably, For example, aliphatic diols, such as linear aliphatic diol and branched aliphatic diol; 36 alkylene ether glycol; alicyclic diol having 4 to 36 carbon atoms; alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO); AO adduct of bisphenols; polylactone diol; polybutadiene diol; carboxyl group Diols having sulfonic acid groups or sulfamic acid groups, and diols having other functional groups such as salts thereof. Among these, an aliphatic diol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic diol is more preferable. These may be used individually by 1 type and may use 2 or more types together.
The content of the linear aliphatic diol with respect to the entire diol is preferably 80 mol% or more, and more preferably 90 mol% or more. When the content is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between the low-temperature fixability and the heat-resistant storage stability is good, and the resin hardness tends to be improved.

The linear aliphatic diol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, Examples include 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.
The branched aliphatic diol having 2 to 36 chain carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,2-propylene glycol, butanediol, hexanediol, octanediol, Examples include decanediol, dodecanediol, tetradecanediol, neopentyl glycol, and 2,2-diethyl-1,3-propanediol.

The alkylene ether glycol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether And glycols.
The alicyclic diol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
There is no restriction | limiting in particular as alkylene oxide (henceforth AO) of the said alicyclic diol, According to the objective, it can select suitably, For example, ethylene oxide (henceforth EO), propylene oxide ( Hereinafter, adducts (number of added moles of 1 to 30) such as butylene oxide (hereinafter abbreviated as BO) and the like can be mentioned.
There is no restriction | limiting in particular as said bisphenol, It can select suitably according to the objective, For example, AO (EO, PO, BO, etc.) addition products (addition mole number 2-such as bisphenol A, bisphenol F, bisphenol S). 30).
There is no restriction | limiting in particular as said polylactone diol, According to the objective, it can select suitably, For example, poly-epsilon-caprolactone diol etc. are mentioned.

There is no restriction | limiting in particular as said diol which has a carboxyl group, According to the objective, it can select suitably, For example, 2, 2- dimethylol propionic acid (DMPA), 2, 2- dimethylol butanoic acid, 2, 2 -Dialkylol alkanoic acids having 6 to 24 carbon atoms such as dimethylol heptanoic acid and 2,2-dimethylol octanoic acid.
The diol having the sulfonic acid group or the sulfamic acid group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N- Sulfamic acid diols such as bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) and AO adduct (AO) As EO or PO, AO addition mole number 1 to 6); bis (2-hydroxyethyl) phosphate and the like can be mentioned.
There is no restriction | limiting in particular as a neutralization base of the diol which has these neutralization bases, According to the objective, it can select suitably, For example, the said C3-C30 tertiary amine (triethylamine etc.), an alkali metal ( Sodium salt).
Among these, alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof are preferable.

  Moreover, there is no restriction | limiting in particular as said trivalent-8 valence or more polyol used as needed, According to the objective, it can select suitably, For example, alkane polyol and its intramolecular or intermolecular dehydration thing (E.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.), saccharides and derivatives thereof (e.g., sucrose, methylglucoside, etc.), etc. Octahydric or higher polyhydric aliphatic alcohols; AO adducts of trisphenols (trisphenol PA, etc.) (addition moles 2-30); AO adducts of novolac resins (phenol novolac, cresol novolac, etc.) (addition) Mole number 2-30); hydroxyethyl (meth) acrylate and other vinyl And acrylic polyols such as a copolymer of monomers. Among these, trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts are preferred, and novolak resin AO adducts are more preferred.

-Polycarboxylic acid-
Examples of the polycarboxylic acid include dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids.
The dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acids such as linear aliphatic dicarboxylic acids and branched aliphatic dicarboxylic acids; aromatic dicarboxylic acids and the like. Are preferable. Among these, linear aliphatic dicarboxylic acid is more preferable.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose.For example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc. Alkane dicarboxylic acids having 4 to 36 carbon atoms; alkenedicarboxylic acids having 4 to 36 carbon atoms such as alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid, maleic acid, fumaric acid and citraconic acid Preferable examples include acids; alicyclic dicarboxylic acids having 6 to 40 carbon atoms such as dimer acid (dimerized linoleic acid).

The aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4 Preferred examples include aromatic dicarboxylic acids having 8 to 36 carbon atoms such as 4,4'-biphenyldicarboxylic acid.
Examples of the trivalent to hexavalent or higher polycarboxylic acid used as necessary include C9-20 aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid.
As the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) are used. It may be used.

  Among the dicarboxylic acids, it is particularly preferable to use the aliphatic dicarboxylic acid (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) alone, but the aromatic dicarboxylic acid and the aromatic Those obtained by copolymerizing an aromatic dicarboxylic acid (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

-Lactone ring-opening polymer-
The lactone ring-opening polymer is not particularly limited and may be appropriately selected according to the purpose. For example, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc. A lactone ring-opening polymer obtained by ring-opening polymerization of lactones such as 12 monolactones (one ester group in the ring) using a metal oxide, an organometallic compound or the like; glycol ( Examples thereof include a lactone ring-opening polymer having a hydroxyl group at the terminal, obtained by ring-opening polymerization of the monolactone having 3 to 12 carbon atoms using ethylene glycol, diethylene glycol, or the like.
There is no restriction | limiting in particular as said C3-C12 monolactone, Although it can select suitably according to the objective, (epsilon) -caprolactone is preferable from a crystalline viewpoint.
In addition, as the lactone ring-opening polymer, a commercially available product may be used. Examples of the commercially available product include highly crystalline polycaprolactones such as H1P, H4, H5, and H7 of the PLACEL series manufactured by Daicel Corporation. Can be mentioned.

-Polyhydroxycarboxylic acid-
There is no restriction | limiting in particular as the preparation method of the said polyhydroxycarboxylic acid, According to the objective, it can select suitably, For example, hydroxycarboxylic acids, such as glycolic acid and lactic acid (L-form, D-form, a racemate, etc.), are directly used. Dehydration condensation method: cyclic ester having 4 to 12 carbon atoms corresponding to dehydration condensate between two or three molecules of hydroxycarboxylic acid such as glycolide, lactide (L-form, D-form, racemate, etc.) Examples of the method include ring-opening polymerization of 2 to 3 ester groups using a catalyst such as a metal oxide or an organometallic compound. The method of ring-opening polymerization is preferable from the viewpoint of adjusting the molecular weight.
Among the cyclic esters, L-lactide and D-lactide are preferable from the viewpoint of crystallinity. These polyhydroxycarboxylic acids may be modified so that the terminal is a hydroxyl group or a carboxyl group.

<Resin connected with crystalline polyester unit>
Examples of a method for obtaining a resin in which a crystalline polyester unit is linked include a method in which a crystalline polyester unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and linked with polyisocyanate. When this means is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased.
Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like.
There is no restriction | limiting in particular as said diisocyanate, According to the objective, it can select suitably, For example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate etc. are mentioned. Among these, the carbon number excluding carbon in the NCO group is 6-20 aromatic diisocyanate, 2-18 aliphatic diisocyanate, 4-15 alicyclic diisocyanate, 8-15 araliphatic diisocyanate, these Preferred is a modified product of diisocyanate (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product), and a mixture of two or more of these. . If necessary, trivalent or higher isocyanates may be used in combination.

  The aromatic diisocyanates are not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6- Tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [formaldehyde and aromatic amine (aniline) or a mixture thereof] Condensation product: phosgenation product of polyaminopolyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4, a mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine ', 4 "-triphenylmethane triisocyanate, m- and p-iso Such Anat phenylsulfonyl isocyanate.

  There is no restriction | limiting in particular as said aliphatic diisocyanate, According to the objective, it can select suitably, For example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane Triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2- And isocyanatoethyl-2,6-diisocyanatohexanoate.

There is no restriction | limiting in particular as said alicyclic diisocyanate, According to the objective, it can select suitably, For example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate. Methyl cyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and 2,6-norbornane diisocyanate.
There is no restriction | limiting in particular as said araliphatic diisocyanate, According to the objective, it can select suitably, For example, m- and p-xylylene diisocyanate (XDI), (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl And xylylene diisocyanate (TMXDI).

The modified diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanate Examples thereof include modified products containing a nurate group and an oxazolidone group. Specifically, modified MDI such as urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, and modified diisocyanates such as urethane-modified TDI such as isocyanate-containing prepolymers; a mixture of two or more of these modified diisocyanates (For example, combined use of modified MDI and urethane-modified TDI).
Among these diisocyanates, aromatic diisocyanates having 6 to 15 carbon atoms excluding carbon in the NCO group, 4 to 12 aliphatic diisocyanates, and 4 to 15 alicyclic diisocyanates are preferable, and TDI, MDI, HDI, Hydrogenated MDI and IPDI are particularly preferred.

<Resin combining crystalline polyester unit and other polymer>
As a method of obtaining a resin in which a crystalline polyester unit and another polymer are bonded, a method in which a crystalline polyester unit and another polymer unit are separately prepared and bonded together, a crystalline polyester unit and another polymer in advance are combined. A method in which one of the units is prepared and then combined by polymerizing the other polymer in the presence of the prepared unit, or a crystalline polyester unit and another polymer unit are simultaneously or sequentially polymerized in the same reaction field However, the first or second method is preferable in that the reaction can be easily controlled as designed.

As the first method, a method in which a unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and connected with polyisocyanate, as in the method for obtaining the resin in which the crystalline polyester unit is connected, is mentioned. It is done. As the polyisocyanate, those described above can be used, and it can also be obtained by introducing an isocyanate group at the terminal of one unit and reacting with the active hydrogen of the other unit. When this means is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased.
As a second method, when the crystalline polyester unit is prepared first, if the next polymer unit to be prepared is an amorphous polyester unit, a polyurethane unit, a polyurea unit or the like, the hydroxyl group at the terminal of the crystalline polyester unit is used. By reacting a group or a carboxyl group with a monomer for obtaining another polymer unit, a resin in which the crystalline polyester unit and another polymer are bonded can be obtained. If the next polymer unit to be produced is a vinyl polymer unit, a vinyl polymerizable double bond is introduced into the crystalline polyester unit in advance to polymerize the vinyl monomer in the presence of the crystalline polyester unit later. By doing so, a resin in which the crystalline polyester unit and another polymer are bonded can be obtained.

<Amorphous polyester unit>
As an amorphous polyester unit, the polycondensation polyester unit synthesize | combined from a polyol and polycarboxylic acid is mentioned, for example. For the polyol and polycarboxylic acid, those exemplified in the above-mentioned crystalline polyester unit can be used. However, in order to design the polymer so as not to have crystallinity, the polymer skeleton should be provided with many bending points and branch points. In order to give an inflection point, for example, bisphenol such as AO (EO, PO, BO, etc.) adduct (addition mole number 2 to 30) such as bisphenol A, bisphenol F, bisphenol S, etc. As the derivative or polycarboxylic acid, phthalic acid, isophthalic acid, or t-butylisophthalic acid may be used. In addition, a trivalent or higher polyol or polycarboxylic acid may be used to introduce the branch point.

<Polyurethane unit>
Examples of the polyurethane unit include a polyurethane unit synthesized from a polyol such as a diol, a trivalent to octavalent or higher polyol, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate. Among these, a polyurethane unit synthesized from the diol and the diisocyanate is preferable.
Examples of the diol and the trivalent to octavalent or higher polyol include those similar to the diol and the trivalent to octavalent or higher polyol cited in the polyester resin.
Examples of the diisocyanate and the trivalent or higher polyisocyanate include the same diisocyanates and trivalent or higher polyisocyanates.

<Polyurea unit>
Examples of the polyurea unit include a polyurea unit synthesized from a polyamine such as a diamine or a trivalent or higher polyamine, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate. Among these, a polyurea unit synthesized from the diamine and the diisocyanate is preferable.
Examples of the diisocyanate and the trivalent or higher polyisocyanate include those similar to the diisocyanate and the trivalent or higher polyisocyanate.

-Polyamine-
Examples of the polyamine include diamines and trivalent or higher polyamines.
There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aliphatic diamines and aromatic diamines are mentioned. Among these, C2-C18 aliphatic diamines and C6-C20 aromatic diamines are preferable. Further, if necessary, the above trivalent or higher amines may be used.

  There is no restriction | limiting in particular as said C2-C18 aliphatic diamine, According to the objective, it can select suitably, For example, carbon, such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc. Alkylene diamine having 2 to 6 carbon atoms; polyalkylene diamine having 4 to 18 carbon atoms such as diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; dialkylaminopropylamine , Alkylene diamines such as trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, and the polyal C1-C4 alkyl or C2-C4 hydroxyalkyl substituted range amine; 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedi C 4-15 alicyclic diamine such as aniline); piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3, C4-C15 heterocyclic diamine such as 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane; xylylenediamine, tetrachloro-p-xylylenediamine And aromatic ring-containing aliphatic amines having 8 to 15 carbon atoms such as amines.

  There is no restriction | limiting in particular as said C6-C20 aromatic diamine, According to the objective, it can select suitably, For example, 1, 2-, 1, 3- and 1, 4- phenylene diamine, 2, 4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m -Unsubstituted aromatic diamines such as aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine; 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltri Range amine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4 4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2 , 5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1 , 5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'- Methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiph Nylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5 An aromatic diamine having a C1-C4 nucleus-substituted alkyl group such as' -tetraisopropyl-4,4'-diaminodiphenylsulfone; the unsubstituted aromatic diamine to the C1-C4 nucleus-substituted alkyl group; Mixtures of various proportions of isomers of aromatic diamines having; methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromodiphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis ( 4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4 -Aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline) ), Aromatic diamines having a nucleus-substituted electron withdrawing group such as 4-aminophenyl-2-chloroaniline (halogens such as Cl, Br, I and F; alkoxy groups such as methoxy and ethoxy; nitro groups and the like); Aromatic diamines having secondary amino groups such as 4'-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene [the unsubstituted aromatic diamine, the nucleus having 1 to 4 carbon atoms] Aromatic diamines having a substituted alkyl group, and mixtures of various ratios of these isomers, and part or all of the primary amino groups of the aromatic diamine having a nucleus-substituted electron withdrawing group are lower alkyl groups such as methyl and ethyl In which the secondary amino group is replaced with a secondary amino group].

  In addition to these, as the diamine, a low molecular weight polyamide obtained by condensation of a dicarboxylic acid (such as a dimer acid) and an excess (more than 2 moles per mole of the acid) the polyamine (the alkylene diamine, the polyalkylene polyamine, etc.). Polyamide polyamines such as polyamines; polyether polyamines such as hydrides of cyanoethylated polyether polyols (polyalkylene glycol and the like).

<Vinyl polymer unit>
The vinyl polymer unit is a polymer unit obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).

(1) Vinyl hydrocarbons:
Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, etc .; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, etc .; terpenes such as pinene, limonene, indene and the like.
Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and salts thereof:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride and its monoalkyl (C1-24) ester, for example, (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino- 2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3 -(Meth) acrylamide-2-hi Roxypropane sulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene, butylene: single, random or block) mono (meth) acrylate sulfate [Poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, etc.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids such as 2-acryloyloxyethylphosphonic acid; and salts thereof.
Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
Amino group-containing vinyl monomers: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, Morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.
Amide group-containing vinyl monomers; (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N-methylene-bis (meth) acrylamide, cinnamon Acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, and the like.
Quaternary ammonium cationic group-containing vinyl monomers: tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide and diallylamine Monomer quaternized product (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate).
Nitro group-containing vinyl monomers: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomer:
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(8) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, Vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) ) Acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (2 Each alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraaryl. Roxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) ac Lilate, lauryl alcohol ethylene oxide 30-mole adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].
Vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, hinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxy Ethyl ether, 3,4-dibutyro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene and the like.
Vinyl ketones, such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, etc.
Vinyl sulfones such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

(9) Other vinyl monomers:
Isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

(10) Fluorine atom element-containing vinyl monomer:
4-fluorostyrene, 2,3,5,6-tetrafluorostyrene, pentafluorophenyl (meth) acrylate, pentafluorobenzyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 2, 2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 4H-hexafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, heptadecafluorodecyl ( Acrylate), trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate 2- (N-butylperfluorooctanesulfonamido) ethyl (meth) acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl (meth) acrylate and the corresponding compounds derived from α-fluoroacrylic acid, bis-hexafluoroisopropyl itaconate, bis-hexafluoroisopropyl maleate, bis-perfluoro Octyl itaconate, bis-perfluorooctyl maleate, bis-trifluoroethyl itaconate and bis-trifluoroethyl maleate, vinyl heptafluorobutyrate, Vinyl perfluoroheptanoate, vinyl perfluorononanoate, vinyl perfluorooctanoate and the like.

  Further, the endothermic amount of the toner in a differential scanning calorimeter (DSC) is preferably 35 to 120 mJ / mg, more preferably 40 to 100 mJ / mg, and further preferably 50 to 80 mJ / mg. The endothermic amount of DSC indicates the amount of the crystalline part that melts during fixing in the toner, and specifically indicates the amount of the crystalline polyester unit part and the release agent. In the present invention, since there are many crystalline parts, the entire toner has sharp melt properties and exhibits low-temperature fixing performance. On the other hand, if the amount of heat absorption is large, the amount of heat necessary for melting the toner at the time of fixing is large, so the low-temperature fixability may be deteriorated, and it is not preferable that the amount of heat absorption is excessive. .

Further, in the diffraction spectrum obtained by the X-ray diffractometer of the toner, when the integrated intensity of the spectrum derived from the crystal structure of the binder resin is (C) and the integrated intensity of the spectrum derived from the amorphous structure is (A). The ratio of (C) / [(C) + (A)] is preferably 0.15 or more from the viewpoint of achieving both fixability and heat-resistant storage stability, more preferably 0.20 or more, and 30 or more is more preferable, and 0.45 or more is particularly preferable. In addition, (C) / [(C) + (A)] is preferably as large as possible, but a practical upper limit for the binder resin used in the toner is about 0.50.
When the toner of the present invention contains a wax, a diffraction peak specific to the wax often appears at a position of 2θ = 23.5 ° to 24 °. However, when the wax content is less than 15% by mass relative to the total weight of the toner, the contribution of the diffraction peak inherent to the wax is negligible. In the case of 15% by mass or more, the value obtained by subtracting the integral intensity of the spectrum derived from the wax crystal structure from the integral intensity of the spectrum derived from the crystal structure of the binder resin is the above-mentioned “crystal structure of the binder resin”. The integrated intensity of the spectrum derived from (C) ”is replaced.

  The ratio (C) / [(C) + (A)] is an index indicating the amount of crystallization sites in the toner (mainly the amount of crystallization sites in the binder resin which is the main component of the toner). . The X-ray diffraction measurement in the present invention is performed using a two-dimensional detector-mounted X-ray diffraction apparatus (D8 DISCOVER with GADDS / Bruker). In addition, a conventionally known toner containing a crystalline resin or wax to the extent of an additive has a ratio of less than about 0.15. For the measurement, a 0.70 mm diameter of a mark tube (Lindenman glass) is used as a capillary tube. The sample is packed up to the top of the capillary tube and measured. Further, tapping is performed when filling the sample, and the number of tapping is 100 times. Detailed measurement conditions are shown below.

・ Tube current: 40 mA
・ Tube voltage: 40 kV
-Goniometer 2θ axis: 20.000 °
-Goniometer Ω axis: 0.0000 °
-Goniometer φ axis: 0.0000 °
・ Detector distance: 15cm (wide angle measurement)
Measurement range: 3.2 ≦ 2θ (°) ≦ 37.2
・ Measurement time: 600 sec

A collimator having a φ1 mm pinhole is used for the incident optical system. The obtained two-dimensional data is integrated with the attached software (chi axis is 3.2 ° to 37.2 °) and converted to one-dimensional data of diffraction intensity and 2θ. A method for calculating the ratio (C) / [(C) + (A)] based on the obtained X-ray diffraction measurement result will be described below.
Examples of diffraction spectra obtained by X-ray diffraction measurement are shown in FIGS. The horizontal axis is 2θ, the vertical axis is the X-ray diffraction intensity, and both are linear axes. In the X-ray diffraction spectrum of FIG. 1, there are main peaks (P1, P2) at 2θ = 21.3 ° and 24.2 °, and a halo (h) is observed in a wide range including these two peaks. Here, the main peak is derived from the crystal structure, and the halo is derived from the amorphous structure.

These two major peaks and halos are transformed into the following Gaussian function:
fp1 (2θ) = ap1exp {− (2θ−bp1) ² / (2cp1) ² } (Formula 1)
fp2 (2θ) = ap2exp {− (2θ−bp2) ² / (2cp2) ² } (Formula 2)
fh (2θ) = ahexp {− (2θ−bh) ² / (2ch) ² } (Formula 3)
(Where fp1 (2θ), fp2 (2θ), and fh (2θ) are functions corresponding to the main peaks P1, P2, and halo, respectively)
The sum of these three functions f (2θ) = fp1 (2θ) + fp2 (2θ) + fh (2θ) (Formula 4)
Is a fitting function (shown in FIG. 2) of the entire X-ray diffraction spectrum, and fitting by the least square method is performed.

There are nine fitting variables, ap1, bp1, cp1, ap2, bp2, cp2, ah, bh, and ch. As initial values of the fitting of each variable, the peak positions of X-ray diffraction (bp1 = 21.3, bp2 = 24.2, bh = 22.5 in the example in the figure) are set in bp1, bp2, and bh, Variables are input as appropriate and values obtained so that the two main peaks and halo are as close as possible to the X-ray diffraction spectrum are set. Fitting can be performed using, for example, Microsoft 2003 Excel 2003 solver.
From the integrated areas (SP1, Sp2, Sh) of fp1 (2θ), fp2 (2θ), and fh (2θ) after fitting, (Sp1 + Sp2) is (C) and Sh is (A). The ratio (C) / [(C) + (A)], which is an index indicating the amount of

[Toner characteristics]
In order to suppress the occurrence of image conveyance flaws, it is preferable that the following condition (1) is satisfied when the maximum exothermic peak temperature under the following conditions is T2 (° C.).
T1-T2 ≦ 30 ° C. and T2 ≧ 30 ° C. (1)

<Measurement method and conditions for maximum heat absorption and heat generation peak of toner>
The maximum endothermic peak of the toner is measured using a DSC system Q-200 (manufactured by TA Instruments). Specifically, first, about 5.0 mg of resin is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, in a nitrogen atmosphere, the temperature was raised from 0 ° C. to 100 ° C. at 10 ° C./min, then the temperature was lowered from 100 ° C. to 10 ° C./min to 0 ° C., and further from 0 ° C. to 10 ° C./min. Let the temperature rise. Using an analysis program in the DSC system Q-200 (manufactured by TA Instruments), a DSC curve at the second temperature rise is selected, and the maximum endothermic peak temperature T1 of the toner is measured. Similarly, the maximum heat generation peak temperature T2 of the toner when the temperature is lowered is measured.

As said T1, 50 to 70 degreeC is preferable, 53 to 65 degreeC is more preferable, and 58 to 62 degreeC is especially preferable. When T1 is 50 ° C. to 70 ° C., the minimum heat-resistant storage stability required for the toner can be ensured, and a toner having excellent low-temperature fixability that is not conventionally obtained can be obtained. When T1 is lower than 50 ° C., the low temperature fixability is improved but the heat resistant storage stability is deteriorated. When T1 is higher than 70 ° C., the heat resistant storage stability is improved, but the low temperature fixability is deteriorated.
T2 is preferably 30 ° C to 55 ° C, more preferably 35 ° C to 55 ° C, and particularly preferably 40 ° C to 55 ° C. If T2 is less than 30 ° C., the speed at which the fixed image is cooled or solidified is slow, and toner image (printed matter) may be blocked or transported. Although T2 is desirably as high as possible, T2 is a crystallization temperature, and thus it is impossible to take a temperature higher than T1, which is the melting point. That is, in order to suppress toner image blocking and conveyance flaws while maintaining excellent heat-resistant storage stability and low-temperature fixability, it is desirable that the difference between T1 and T2 (T1-T2) is within a certain range. T1-T2 is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, and particularly preferably 20 ° C. or lower. When T1-T2 is higher than 40 ° C., the difference between the fixing temperature and the temperature at which the toner image is solidified is large, and the effect of suppressing toner image blocking and conveyance flaws cannot be obtained.

For toners that contain crystalline resin as the main component of binder resin, the property of sharply decreasing viscoelasticity above the melting point that was previously considered effective for low-temperature fixability (sharp melt properties) can be fixed depending on the paper type. It is considered that the temperature range is greatly different. Therefore, as a binder resin used in a conventional toner having excellent low-temperature fixability, a certain amount of a component having a high molecular weight, specifically, a component having a molecular weight in terms of polystyrene in gel diffusion chromatography (GPC) of 100,000 or more. In order to enable fixing at a constant temperature and a constant speed regardless of the type of paper, it is preferable that the above-mentioned content and the weight average molecular weight be within a certain range.
The component having a molecular weight of 100,000 or more is preferably contained in an amount of 5% by mass or more, more preferably 7% by mass or more, and further preferably 9% by mass or more. When 5% by mass or more of a component having a molecular weight of 100,000 or more is contained, the temperature dependency of the fluidity and viscoelasticity of the toner after melting is reduced, so that heat is transferred to the toner even in thin paper where the heat is easily transferred to the toner during fixing. Even a difficult thick paper is unlikely to have a great difference in toner fluidity and elastic modulus, and the fixing device can be fixed at a constant temperature and at a constant speed. If the component having a molecular weight of 100,000 or more is less than 5% by mass, the fluidity and viscoelasticity after melting the toner vary greatly depending on the temperature. For example, in the fixing on thin paper, the deformability of the toner becomes too large and the adhesion area to the fixing member As a result, particularly when the fixing member becomes high temperature, the release from the fixing member cannot be performed well, and paper wrapping may occur.

The reason why the above effect can be obtained is considered as follows. That is, the crystalline resin has a sharp melt property as described above, but the internal cohesive force and viscoelasticity of the toner in a molten state vary greatly depending on the molecular weight and structure of the resin. For example, when it has a urethane bond or urea bond, which is a linking group having a large cohesive energy, it behaves like an elastic body such as rubber at a relatively low temperature even when melted, while the polymer chain becomes As thermal kinetic energy increases, the agglomeration between bonds gradually dissolves and approaches a viscous body.
When such a resin is used as a binder resin for toner, even if the fixing can be performed without problems when the fixing temperature is low, the internal cohesive force when the toner is melted is small when the fixing temperature is high. A so-called hot offset phenomenon in which the side adheres to the fixing member may occur, and the image quality is significantly impaired. Increasing the number of urethane bonds and urea bonding sites to avoid hot offset can be fixed without any problems at high temperatures. On the other hand, when fixing at low temperatures, the image gloss becomes low and the paper is melted and impregnated. Becomes insufficient and the image is likely to be detached from the paper. In particular, when fixing to paper with a large thickness and uneven surface, the heat transfer efficiency to the toner at the time of fixing is low, and the fixing state is further deteriorated. Is not sufficiently applied, the fixing state of the toner, which is particularly in an elastic state, is remarkably deteriorated.

  When the molecular weight is considered as a means for controlling the viscoelasticity after melting, as a matter of course, the larger the molecular weight, the more obstacles to the movement of the molecular chain, so the viscoelasticity increases. Further, when the molecular weight is large, entanglement occurs, and thus elastic behavior is exhibited. Considering the fixability on paper, a smaller molecular weight is preferable because the viscosity at the time of melting is lower, but hot offset occurs if there is no elasticity. However, if the molecular weight is increased as a whole, the fixability is deteriorated, and particularly in the case of thick paper, the heat transfer efficiency to the toner at the time of fixing is low, so that the fixing state is further deteriorated. Therefore, the viscoelasticity after melting can be suitably controlled by including a high molecular weight crystalline component while preventing the molecular weight of the binder resin as a whole from becoming too large, and can be used for paper types such as thin paper and cardboard. Regardless, a toner that can be fixed at a constant temperature and at a constant speed can be obtained.

  The range of the weight average molecular weight is preferably 20,000 to 70,000, more preferably 30,000 to 60,000, and particularly preferably 35,000 to 50,000. When the weight average molecular weight exceeds 70,000, the whole binder resin is too high in molecular weight, so that the fixing property is deteriorated, the gloss is too low, and the image after fixing is easily lost due to external stress. . On the other hand, if the amount is less than 20,000, no matter how much high molecular weight component is present, the internal cohesive force at the time of melting the toner becomes too low, causing hot offset and paper wrapping around the fixing member. It is not preferable.

Examples of a method for obtaining a toner containing a binder resin having a molecular weight distribution as described above include a method using two or more types of resins having different molecular weight distributions, and a method using a resin whose molecular weight distribution is controlled during polymerization. It is done.
When two or more kinds of resins having different molecular weight distributions are used in combination, at least two kinds of relatively high molecular weight resins and low molecular weight resins are used. As the high molecular weight resin, a resin having a large molecular weight may be used in advance, or a modified resin having an isocyanate group at the terminal may be elongated in the production process of the toner to form a high molecular weight body. In the latter method, the high molecular weight material can be uniformly present in the toner, and in the production method in which the binder resin is dissolved in the organic solvent, it is more soluble than the high molecular weight resin from the beginning. Since it is easy to make it, it is preferable.
The ratio of the high molecular weight resin (including a modified resin having an isocyanate group) and the low molecular weight resin as the binder resin is such that the ratio of the high molecular weight resin / low molecular weight resin is 5 / 95-60 / 40, preferably 8 / 92-50 / 50, more preferably 12 / 88-35 / 65, still more preferably 15 / 85-25 / 75. When the number of high molecular weight substances is less than 5/95, or when the number of high molecular weight substances is larger than 60/40, it becomes difficult to obtain a toner having a binder resin having the molecular weight distribution described above.

  When using a resin whose molecular weight distribution is controlled at the time of polymerization, as a method for obtaining such a resin, for example, in the case of a polymerization form such as polycondensation, polyaddition or addition condensation, in addition to a bifunctional monomer The molecular weight distribution can be broadened by adding a small amount of monomers having different numbers of functional groups. Monomers with different numbers of functional groups include tri- or higher-functional monomers and mono-functional monomers. However, when tri- or higher-functional monomers are used, a branched structure is generated. May be difficult to form. If a monofunctional monomer is used, the polymerization reaction is stopped by the monomer, so that the low molecular weight resin in the case of using two or more resins is purified, and a part of the polymerization reaction proceeds to become a high molecular weight component. .

  In the present invention, the tetrahydrofuran-soluble content of the toner and the molecular weight distribution and weight average molecular weight (Mw) of the resin are measured using a gel permeation chromatography (GPC) measuring device (for example, HLC-8220 GPC: manufactured by Tosoh Corporation). it can. As a column, TSKgel SuperHZM-H 15 cm triple (made by Tosoh Corporation) is used. The resin to be measured is made into a 0.15 mass% solution with tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate is used as a sample. 100 μL of the THF sample solution is injected into a measuring apparatus, and measurement is performed at a flow rate of 0.35 mL / min in an environment at a temperature of 40 ° C.

The molecular weight is calculated using a calibration curve prepared from a monodisperse polystyrene standard sample. As the standard polystyrene sample, ShowdexSTANDARD series manufactured by Showa Denko KK and toluene are used. The following three types of THF solutions of monodisperse polystyrene standard samples are prepared, measured under the above conditions, and a calibration curve is created using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample.
-Solution A: S-7450 2.5 mg, S-678 2.5 mg, S-46.5 2.5 mg, S-2.90 2.5 mg, THF 50 mL
-Solution B: S-3730 2.5 mg, S-257 2.5 mg, S-19.8 2.5 mg, S-0.580 2.5 mg, THF 50 mL
-Solution C: S-1470 2.5 mg, S-112 2.5 mg, S-6.93 2.5 mg, Toluene 2.5 mg, THF 50 mL
An RI (refractive index) detector is used as the detector.
The ratio of the component having a molecular weight of 100,000 or more and the ratio of the component having a molecular weight of 250,000 or more can be examined from the intersection of the molecular weight of 100,000 and the molecular weight of 250,000 in the integral molecular weight distribution curve.

The high molecular weight component needs to have a resin structure close to that of the entire binder resin. If the binder resin has crystallinity, the high molecular weight component also needs to have crystallinity. When the high molecular weight component is significantly different in structure from the other resin components, the polymer is easily phase-separated and becomes a sea-island state, so that it cannot be expected to contribute to improvement of viscoelasticity and cohesive force on the whole toner. As a comparison of the degree of crystalline structure content between the high molecular weight component and the whole binder resin, for example, differential scanning of insolubles in a mixed solvent of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by weight). The ratio [ΔH (H) / ΔH (T)] of the endothermic amount [ΔH (H)] in the calorimeter (DSC) and the endothermic amount [ΔH (T)] in the DSC of the toner is 0.2 to 1.25. Preferably, it is in the range of 0.3 to 1.0, more preferably in the range of 0.4 to 0.8.
In order to obtain an insoluble content in a mixed solvent of THF and ethyl acetate (mixing ratio is 50:50 by weight), 0.4 g of toner is added to 40 g of the above mixed solvent at normal temperature (20 ° C.) and shaken for 20 minutes. After mixing, what is necessary is just to vacuum-dry the thing which settled the insoluble component with the centrifuge and removed the supernatant liquid.

<Colorant>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably from well-known dyes and pigments. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow ( GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Iso Indolinone Yellow, Bengala, Pangdan, Lead Red, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilli Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon , Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine oren , Perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, Ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Examples include zinc white and litbon. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a color of the said colorant, According to the objective, it can select suitably, For example, the colorant for colors, such as a colorant for black, magenta, cyan, yellow, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black colorant include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), Examples thereof include metals such as titanium oxide and organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta colorant include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

Examples of the colorant for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.
Examples of the colorant for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner is decreased. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, and the coloring power decreases and the electrical characteristics of the toner decrease. May be invited.

  The colorant may be used as a master batch combined with a resin. There is no restriction | limiting in particular as this resin, According to the objective, it can select suitably from well-known things. For example, styrene or its substituted polymer, styrene copolymer, polymethyl methacrylate resin, polybutyl methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy Polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin Etc. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene resin, poly-p-chlorostyrene resin, and polyvinyl toluene resin. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - like maleic acid ester copolymer.
These masterbatch resins are not a problem even if they are crystalline resins in the present invention.

The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant with a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it.
The flushing method is a method of mixing or kneading an aqueous paste containing water as a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components.
For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.
The toner of the present invention may be used as a clear toner containing no pigment for the purpose of making the gloss and texture of an image uniform, for designs such as watermark images, and other purposes.

<Charge control agent>
The toner of the present invention may contain a charge control agent as necessary. The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may be changed when a colored material is used, a colorless or nearly white material is preferable. Examples of such charge control agents include triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Examples thereof include a simple substance or a compound thereof, a simple substance of tungsten or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products may be used as the charge control agent. For example, quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenol condensation E-89 (both manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, LR-147 which is a boron complex (manufactured by Nippon Carlit) ); Quinacridone, azo pigments, other sulfonic acid groups, carboxyl groups, four Examples thereof include polymer compounds having a functional group such as a quaternary ammonium salt.

The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when dissolved or dispersed, or the toner surface after the toner particles are produced. It may be fixed to.
The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of the additive, the dispersion method, and the like, and cannot be generally specified. 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. If the content is less than 0.1 parts by mass, the charge controllability may not be obtained. If the content exceeds 10 parts by mass, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

<External additive>
The toner of the present invention may use an external additive as necessary. The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, Metal oxide (for example, titanium oxide, alumina, tin oxide, antimony oxide, etc.), hydrophobized metal oxide fine particles, fluoropolymer, and the like. Among these, hydrophobized silica fine particles, hydrophobized titanium oxide fine particles, and hydrophobized alumina fine particles are preferable.

Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil Co., Ltd.). Examples of the titanium oxide fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), Examples thereof include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T ( All are manufactured by Fuji Titanium Industry Co., Ltd .;
Hydrophobized silica fine particles, hydrophobized titanium oxide fine particles, hydrophobized alumina fine particles are silica fine particles, titanium oxide fine particles, hydrophilic fine particles such as alumina fine particles, methyltrimethoxysilane, methyltriethoxysilane, It can be obtained by treatment with a silane coupling agent such as octyltrimethoxysilane.

Further, as the external additive, silicone oil-treated inorganic fine particles obtained by treating inorganic fine particles with silicone oil (by applying heat if necessary) are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic or methacryl modified silicone oil, α-methylstyrene modified silicone oil, etc. can be used. .

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Examples include wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.

The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 to 3% by mass with respect to the toner.
The mass average particle size of primary particles of the inorganic fine particles is preferably 3 to 70 nm. When the mass average particle size is less than 3 nm, the inorganic fine particles are buried in the toner, and the function thereof is not easily exhibited. On the other hand, if the thickness exceeds 70 nm, the surface of the electrostatic latent image carrier is undesirably damaged.
As the external additive, the inorganic fine particles or the hydrophobic treated inorganic fine particles can be used in combination. The number average particle size of the hydrophobized primary particles is preferably 1 to 100 nm, and more preferably 5 to 70 nm. More preferably, two or more kinds of inorganic fine particles are contained. Further, it is more preferable that at least two kinds of inorganic fine particles having a number average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment and at least one kind of inorganic fine particles of 30 nm or more are contained. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

  Examples of the surface treatment agent for the external additive containing fine oxide particles include silane coupling agents such as dialkyl dihalogenated silane, trialkyl halogenated silane, alkyl trihalogenated silane, and hexaalkyldisilazane, silylating agents, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and silicone varnish.

  Resin fine particles can also be added as the external additive. Examples of the resin fine particles include polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization; copolymers of methacrylic acid esters and acrylic acid esters; polycondensation polymer particles such as silicone, benzoguanamine, and nylon; Examples thereof include polymer particles made of a thermosetting resin. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the toner.

<Fluidity improver>
The fluidity improver means a material that can improve the hydrophobicity by surface treatment of the toner, and can prevent deterioration of the flow characteristics and charging characteristics of the toner even under high humidity. For example, a silane coupling agent, silylated Agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like.

<Cleaning improver>
The toner of the present invention may use a cleaning improver if necessary. The cleaning property improving agent is added to the toner in order to remove the developer after transfer remaining on the electrostatic latent image bearing member or the intermediate transfer member. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid; polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a mass average particle size of 0.01 to 1 μm are suitable.

<Magnetic material>
The toner of the present invention can be used as a non-magnetic one-component developer or a two-component developer by mixing with a carrier, and can also be used as a magnetic toner containing a magnetic material. There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

<Career>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers a core material is preferable.
−Core material−
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, 50-90 emu / g manganese-strontium type material, 50-90 emu / g manganese-magnesium type material etc. Can be mentioned. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. .
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular in the volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10-150 micrometers is preferable and 40-100 micrometers is more preferable. If the volume average particle size is less than 10 μm, fine particles are increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. If it exceeds 150 μm, the specific surface area is decreased, and In the case of a full color with many solid portions, the reproduction of the solid portions may be deteriorated.
When toner is used for a two-component developer, it may be used by mixing with the carrier. There is no restriction | limiting in particular in content of the said carrier in the said two-component developer, Although it can select suitably according to the objective, 90-98 mass parts is preferable with respect to 100 mass parts of said two-component developers. 93 to 97 parts by mass are more preferable.

The toner of the present invention forms an electrostatic latent image by exposing the surface of the electrostatic latent image carrier, the charging means for charging the surface of the electrostatic latent image carrier, and the charged electrostatic latent image carrier surface. Exposure means; development means for developing the electrostatic latent image with toner to form a visible image; transfer means for transferring the visible image to a recording medium; and a transfer image transferred to the recording medium. Can be suitably used in an image forming apparatus or an image forming method having at least a fixing unit for fixing the toner.
The image forming apparatus further includes at least an electrostatic latent image carrier and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. It can be used as a toner for a process cartridge that can be attached to and detached from the main body.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the examples, “part” is “part by mass”.

<Measurement of melting point, half width of endothermic peak, glass transition temperature (Tg)>
The melting point and Tg of each material were measured as follows using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). Moreover, based on these measurement data, the half value width of the endothermic peak was derived as follows.
About 10 mg of the sample was placed in an aluminum sample container, which was placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, and then the sample was cooled to room temperature and left for 10 minutes, and again raised to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at a temperature rate of 10 ° C./min.
Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system. In addition, a line segment is drawn perpendicularly to the baseline from the endothermic peak, and the temperature difference between the two points where the line passing through the center of the line segment and parallel to the baseline intersects the temperature-calorie plot is the half-value width of the endothermic peak. It was.

<Measurement of content of linear monoester having 48 or more carbon atoms>
The content of linear monoester having 48 or more carbon atoms was measured by gas chromatography (GC) as follows. The GC apparatus used was 6890N manufactured by Agilent, the column used Ultra Alloy-1 (HT) having an inner diameter of 0.5 mm and a length of 10 m, and the detector used 5975 MSD manufactured by Agilent.
The column is heated from 40 ° C. to 200 ° C. at a heating rate of 40 ° C./min, then heated to 350 ° C. at a heating rate of 15 ° C./min, and further 450 at a heating rate of 7 ° C./min. The temperature was raised to ° C. The detection condition was Scan mode, and m / z was 35 to 700.
The measurement was performed by driving a sample obtained by dissolving 0.1 g of sample in 10 mL of toluene into GC. The structure of the component was identified from the fragment pattern and retention time of the detected peak. The total peak area of a linear monoester having 48 or more carbon atoms divided by the area of all peaks in the total ion chromatogram (TIC) is the content of the linear monoester having 48 or more carbon atoms. did.

<Preparation of crystalline resin 1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 241 parts of sebacic acid, 31 parts of adipic acid, 164 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 75 parts were added and reacted for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream, and under reduced pressure of 5-20 mmHg, Mw (mass average molecular weight) ) To reach about 18,000 to obtain [Crystalline Resin 1] (crystalline polyester resin) having a melting point of 58 ° C.

<Preparation of crystalline resin 2>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 283 parts of sebacic acid, 215 parts of 1,6-hexanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were placed, and a nitrogen stream The reaction was carried out at 180 ° C. for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw is about 17, under a reduced pressure of 5 to 20 mmHg. It was made to react until it reached 000, and [crystalline resin 2] (crystalline polyester resin) having a melting point of 63 ° C. was obtained.

<Preparation of crystalline resin 3>
322 parts of dodecanedioic acid, 215 parts of 1,6-hexanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The reaction was carried out for 8 hours at 180 ° C. while distilling off the produced water under an air stream. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and under a reduced pressure of 5 to 20 mmHg, the Mw is about 6, The reaction was allowed to reach 000.
269 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 280 parts of ethyl acetate and 85 parts of tolylene diisocyanate (TDI) were added, and the mixture was heated at 80 ° C. under a nitrogen stream. For 5 hours. Next, ethyl acetate was distilled off under reduced pressure to obtain [Crystalline Resin 3] (crystalline polyurethane resin) having an Mw of about 18,000 and a melting point of 68 ° C.

<Preparation of crystalline resin 4>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 283 parts of sebacic acid, 215 parts of 1,6-hexanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were placed, and a nitrogen stream The reaction was carried out at 180 ° C. for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and under a reduced pressure of 5 to 20 mmHg, the Mw is about 6, The reaction was allowed to reach 000.
249 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 250 parts of ethyl acetate and 82 parts of hexamethylene diisocyanate (HDI) were added, and the mixture was heated at 80 ° C. under a nitrogen stream. For 5 hours. Next, ethyl acetate was distilled off under reduced pressure to obtain [Crystalline Resin 4] (crystalline polyurethane resin) having an Mw of approximately 20,000 and a melting point of 65 ° C.

<Preparation of crystalline resin 5>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 283 parts of sebacic acid, 215 parts of 1,6-hexanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were placed, and a nitrogen stream The reaction was carried out at 180 ° C. for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw is about 7, under a reduced pressure of 5 to 20 mmHg. The reaction was allowed to reach 000.
200 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and 280 parts of ethyl acetate, 92 parts of 4,4'-diphenylmethane diisocyanate (MDI), bisphenol A ethylene oxide. 50 parts of a 2 mol adduct was added and reacted at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain [Crystalline Resin 5] (crystalline polyurethane resin) having an Mw of about 27,000 and a melting point of 68 ° C.

<Preparation of crystalline resin 6>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 283 parts of sebacic acid, 215 parts of 1,6-hexanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were placed, and a nitrogen stream The reaction was carried out at 180 ° C. for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol generated under a nitrogen stream, and under a reduced pressure of 5 to 20 mmHg, the Mw was about 39, It was made to react until it reached 000, and [crystalline resin 6] (crystalline polyester resin) having a melting point of 65 ° C. was obtained.

<Preparation of Amorphous Resin 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen insertion tube, 219 parts of bisphenol A ethylene oxide 2 mol adduct, 130 parts of bisphenol A propylene oxide 2 mol adduct, 26 parts terephthalic acid, 140 parts isophthalic acid, and 0.5 part of tetrabutoxy titanate was added, and the reaction was allowed to proceed for 8 hours while distilling off the generated water under a nitrogen stream at 230 ° C. and normal pressure. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When the acid value becomes 2, it is cooled to 180 ° C., 35 parts of trimellitic anhydride is added, and the reaction is carried out at normal pressure for 3 hours. ] Was obtained. The obtained [Non-crystalline resin 1] had Mw 9,100 and Tg 62 ° C.

<Preparation of prepolymer A of crystalline resin>
247 parts of hexamethylene diisocyanate (HDI) and 247 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and 249 parts of [Crystalline Resin 4] are dissolved in 249 parts of ethyl acetate. The obtained resin solution was added and reacted at 80 ° C. for 5 hours under a nitrogen stream to obtain a 50% by mass ethyl acetate solution of [crystalline resin prepolymer A] (modified polyurethane resin) having an isocyanate group at the terminal.

<Preparation of non-crystalline resin prepolymer B>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted under reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester]. This [intermediate polyester] had a number average molecular weight of 2100, Mw of 9500, Tg of 55 ° C., an acid value of 0.5 and a hydroxyl value of 49.
Next, 411 parts of [intermediate polyester], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Prepolymer B] was obtained.
[Amorphous resin prepolymer B] had a free isocyanate content of 1.53% by mass.

<Preparation of synthetic ester wax 1>
362 parts of stearyl alcohol and 638 parts of melicic acid are put into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 200 ° C. for 20 hours while distilling water out of the system in a nitrogen atmosphere. Then, the mixture was cooled to 80 ° C., a mixed solvent of toluene and ethanol was added, an aqueous potassium hydroxide solution was further added, and the mixture was stirred for 30 minutes. Next, the aqueous phase was removed, washed with ion-exchanged water three times, and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 1].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 1] was 99% by mass, the melting point was 79 ° C., and the half value width of the endothermic peak was 8 ° C.

<Preparation of synthetic ester wax 2>
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 408 parts of behenyl alcohol and 595 parts of melicic acid are added and reacted at 220 ° C. for 18 hours while distilling water out of the system in a nitrogen atmosphere. After cooling to 80 ° C., a mixed solvent of toluene and ethanol was added, and an aqueous potassium hydroxide solution was further added, followed by stirring for 30 minutes. Next, the aqueous phase was removed, washed with ion-exchanged water three times, and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 2].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 2] was 100% by mass, the melting point was 83 ° C., and the half-value width of the endothermic peak was 8 ° C.

<Preparation of synthetic ester wax 3>
474 parts of behenyl alcohol and 525 parts of behenic acid are put into a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, and reacted at 220 ° C. for 18 hours while distilling water out of the system in a nitrogen atmosphere. After cooling to 80 ° C., a mixed solvent of toluene and ethanol was added, and an aqueous potassium hydroxide solution was further added, followed by stirring for 30 minutes. Next, the aqueous phase was removed, washed with ion-exchanged water three times, and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 3].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 3] was 0% by mass, the melting point was 70 ° C., and the half value width of the endothermic peak was 7 ° C.

<Preparation of synthetic ester wax 4>
438 parts of behenyl alcohol, 225 parts of behenic acid, and 337 parts of melicic acid were put into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and 220 ° C. while distilling water out of the system in a nitrogen atmosphere. Then, the mixture was cooled to 80 ° C., a mixed solvent of toluene and ethanol was added, an aqueous potassium hydroxide solution was further added, and the mixture was stirred for 30 minutes. Next, the aqueous phase was removed, washed with ion-exchanged water three times, and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 4].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 4] was 60% by mass, the melting point was 75 ° C., and the half value width of the endothermic peak was 9 ° C.

<Preparation of synthetic ester wax 5>
447 parts of behenyl alcohol, 320 parts of behenic acid and 232 parts of melicic acid were put into a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, and 220 ° C. while distilling water out of the system in a nitrogen atmosphere. Then, the mixture was cooled to 80 ° C., a mixed solvent of toluene and ethanol was added, an aqueous potassium hydroxide solution was further added, and the mixture was stirred for 30 minutes. Next, the aqueous phase was removed, washed with ion-exchanged water three times, and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 5].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 5] was 42% by mass, the melting point was 74 ° C., and the half value width of the endothermic peak was 10 ° C.

<Preparation of synthetic ester wax 6>
454 parts of behenyl alcohol, 354 parts of behenic acid, and 197 parts of melicic acid were put into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and 220 ° C. while distilling water out of the system in a nitrogen atmosphere. Then, the mixture was cooled to 80 ° C., a mixed solvent of toluene and ethanol was added, an aqueous potassium hydroxide solution was further added, and the mixture was stirred for 30 minutes. Next, the aqueous phase was removed, washed with ion-exchanged water three times, and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 6].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 6] was 35% by mass, the melting point was 72 ° C., and the half-value width of the endothermic peak was 9 ° C.

<Preparation of synthetic ester wax 7>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction pipe, 61 parts of ethylene glycol and 951 parts of melicic acid are charged and reacted at 180 ° C. for 24 hours while distilling water out of the system in a nitrogen atmosphere. After cooling to 80 ° C., a mixed solvent of toluene and ethanol was added, and an aqueous potassium hydroxide solution was further added, followed by stirring for 30 minutes. Next, the aqueous phase was removed, washed with ion-exchanged water three times, and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 7].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 7] was 0% by mass, the melting point was 72 ° C., and the half value width of the endothermic peak was 10 ° C.

<Preparation of synthetic ester wax 8>
342 parts of behenyl alcohol, 85 parts of stearyl alcohol, 254 parts of behenic acid and 310 parts of melicic acid are put into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and water is kept outside the system in a nitrogen atmosphere. The reaction was carried out at 200 ° C. for 0 hour while cooling, then cooled to 80 ° C., a mixed solvent of toluene and ethanol was added, then an aqueous potassium hydroxide solution was added and stirred for 30 minutes, and the aqueous phase was removed. , Washed 3 times with on-exchange water, and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 8].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 8] was 44% by mass, the melting point was 68 ° C., and the half-value width of the endothermic peak was 11.1 ° C.

<Preparation of synthetic ester wax 9>
342 parts of behenyl alcohol, 85 parts of stearyl alcohol, 254 parts of behenic acid and 310 parts of melicic acid are put into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and water is removed from the system under a nitrogen atmosphere. After reacting at 200 ° C. for 17 hours while distilling off, the mixture was cooled to 80 ° C., a mixed solvent of toluene and ethanol was added, an aqueous potassium hydroxide solution was further added and stirred for 20 minutes, and then the aqueous phase was removed. Furthermore, it was washed once with ion-exchanged water and dried under reduced pressure at 190 ° C. to obtain [Synthetic ester wax 9].
The content of linear monoester having 48 or more carbon atoms in [Synthetic ester wax 9] was 41% by mass, the melting point was 64 ° C., and the half value width of the endothermic peak was 14.4 ° C.

<Preparation method of colorant dispersion>
In a beaker, 20 parts of copper phthalocyanine, 4 parts of a colorant dispersant (Solspers 28000; manufactured by Avisia) and 76 parts of ethyl acetate were stirred and uniformly dispersed. Then, copper phthalocyanine was finely dispersed by a bead mill. [Colorant dispersion 1] was obtained.
The volume average particle diameter of [Colorant Dispersion Liquid 1] measured with a particle diameter measuring apparatus LA-920 (manufactured by Horiba Seisakusho) was 0.3 μm.

<Preparation of release agent dispersion 1>
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 15 parts of [synthetic ester wax 1] and 85 parts of ethyl acetate are added and heated to 78 ° C. to dissolve sufficiently. Then, using Ultraviscomil (manufactured by Imex Co., Ltd.), liquid feeding speed 1.0 Kg / hr, disk peripheral speed: 10 m / sec, 0.5 mm zirconia bead filling 80 volume%, number of passes 6 times Wet pulverized under the following conditions. Finally, ethyl acetate was added and adjusted so that the solid content concentration was 15% by mass to obtain [Releasing Agent Dispersion Liquid 1].

<Preparation of release agent dispersions 2-7>
Except that the [Synthetic ester wax 1] was changed to [Synthetic ester wax 2-7], [Release agent dispersions 2-7] were obtained in the same manner as the release agent dispersion liquid 1.

<Preparation of release agent dispersion 8>
Except for the point that [synthetic ester wax 1] was changed to sunflower wax (content of straight chain monoester having 48 or more carbon atoms, 53 mass%, melting point 78 ° C., half-value width 6.6 ° C. of endothermic peak). [Mold release agent dispersion 8] was obtained in the same manner as in the case of mold release dispersion 1.

<Preparation of release agent dispersion 9>
Mold release agent except that [Synthetic ester wax 1] was changed to paraffin wax (content of linear monoester having 48 or more carbon atoms, 0 mass%, melting point 76 ° C., half-value width of endothermic peak 3.9 ° C.) [Releasing agent dispersion 9] was obtained in the same manner as in dispersion 1.

<Preparation of mold release agent dispersion 10>
Except that the [Synthetic ester wax 1] was changed to [Synthetic ester wax 8], [Mold release agent dispersion 10] was obtained in the same manner as the mold release agent dispersion 1.

<Preparation of release agent dispersion 11>
Except for the point that [Synthetic ester wax 1] was changed to [Synthetic ester wax 9], [Mold release agent dispersion 11] was obtained in the same manner as in the case of the mold release agent dispersion 1.

(Preparation of resin solutions 1 to 6)
In a reaction vessel equipped with a thermometer and a stirrer, 100 parts of [Crystalline Resin 1-6] and 100 parts of ethyl acetate are added, heated to 50 ° C. and stirred to obtain a homogeneous phase [Resin Solutions 1-6] Got.

-Production of carrier A-
As a core material, 5,000 parts of Mn ferrite particles (mass average diameter: 35 μm), and as a coating material, 450 parts of toluene, 472 parts of a silicone resin SR2400 (manufactured by Toray Dow Corning Silicone, non-volatile content 50% by mass), Using a coating solution prepared by dispersing 11 parts of aminosilane SH6020 (manufactured by Toray Dow Corning Silicone) and 12 parts of carbon black with a stirrer for 15 minutes, the core material and this coating solution are rotated in a fluidized bed. The coating liquid was applied to the core material by applying the coating liquid while forming a swirling flow provided with a bottom plate disk and stirring blades. The obtained coated material was baked in an electric furnace at 250 ° C. for 3 hours to obtain [Carrier A].

[Example 1]
In a beaker, 45 parts of [resin solution 3], 15 parts of [resin solution 6], 14 parts of [release agent dispersion 1] and 10 parts of [colorant dispersion 1] are placed at 50 ° C. with a TK homomixer. Was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [Toner Material Liquid 1].
On the other hand, 99 parts of ion-exchanged water in a beaker and 25% by mass aqueous dispersion of organic resin fine particles for dispersion stabilization (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). 6 parts of a solution, 1 part of sodium carboxymethylcellulose, and 10 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, Ltd .: Eleminol MON-7) were uniformly dissolved. Next, 75 parts of [Toner Material Liquid 1] were added at 50 ° C. while stirring the TK homomixer at 10,000 rpm, and stirred for 2 minutes.
Next, this mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 55 ° C. until the concentration became 0.5% by mass or less, and [Aqueous resin dispersion 1 of resin particles] was obtained. Obtained.
Next, as a pre-cleaning step, [Aqueous resin dispersion 1 of resin particles] was cooled to room temperature, filtered, and 300 parts of ion-exchanged water was added to the obtained filter cake, and a TK homomixer was used. The mixture was filtered at 12,000 rpm for 10 minutes and then filtered twice.
Next, 300 parts of ion-exchanged water is added to the obtained filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, the operation of filtering is performed three times. 300 parts by mass of hydrochloric acid was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered. Finally, 300 parts of ion-exchanged water was added to the obtained filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, the operation of filtering was performed twice to obtain a filter cake.
The obtained cake was crushed and then dried at 40 ° C. for 22 hours to obtain [Resin Particle 1] having a volume average particle size of 5.6 μm.
100 parts of the obtained [resin particles 1] and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were used at a peripheral speed of 30 m / h using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After 5 cycles of mixing for 30 seconds in seconds and resting for 1 minute, a sieve having a mesh opening of 35 μm was sieved to prepare toner 1. The content of the release agent in the toner 1 was 4% by mass.

[Example 2]
[Resin particle 2] was obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] in Example 1 was changed to [Releasing agent dispersion 2]. Produced.

[Example 3]
[Resin particles 3] were obtained in the same manner as in Example 1 except that [Releasing Agent Dispersion 1] in Example 1 was changed to [Releasing Agent Dispersion 4]. Produced.

[Example 4]
[Resin particle 4] was obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] in Example 1 was changed to [Releasing agent dispersion 5]. Produced.

[Example 5]
[Resin particles 5] were obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] in Example 1 was changed to [Releasing agent dispersion 8]. Produced.

[Example 6]
[Resin particle 6] was obtained in the same manner as in Example 5 except that the number of parts of [Releasing Agent Dispersion Liquid 8] in Example 5 was changed from 14 parts to 49 parts, and toner 6 was produced using this. did. The content of the release agent in the toner 6 was 14% by mass.

[Example 7]
[Resin particles 7] were obtained in the same manner as in Example 5 except that the number of parts of [Releasing Agent Dispersion Liquid 8] in Example 5 was changed from 14 parts to 7 parts, and toner 7 was produced using this. did. The content of the release agent in the toner 7 was 2% by mass.

[Example 8]
[Resin particle 8] was obtained in the same manner as in Example 1 except that [Resin solution 3] in Example 1 was changed to [Resin solution 1], and toner 8 was produced using this.

[Example 9]
[Resin particle 9] was obtained in the same manner as in Example 4 except that [Resin solution 6] in Example 4 was changed to [Prepolymer A of crystalline resin], and toner 9 was produced using this.

[Example 10]
[Resin particle 10] was obtained in the same manner as in Example 9, except that [Resin solution 3] in Example 9 was changed to [Resin solution 5], and toner 10 was produced using this.

[Example 11] (Aggregating toner)
(Preparation of crystalline resin latex 1)
[Crystalline Resin 1] 40 g was added to 360 g of ion-exchanged water, heated to 90 ° C., adjusted to pH = 7.5 with 4 mass% sodium hydroxide aqueous solution, 10 mass% dodecylbenzenesulfonic acid aqueous solution 0. While adding 8 g, the mixture was stirred at 8000 rpm using an Ultra Turrax T50 manufactured by IKA to produce a crystalline resin latex 1 having a center diameter of 320 nm. The solid content concentration of the latex was 11% by mass.

(Preparation of crystalline resin latex 2)
1.1 g of 10% by mass dodecylbenzenesulfonic acid aqueous solution is added to 360 g of ion-exchanged water, and further adjusted to pH = 9.0 with 4% by mass sodium hydroxide aqueous solution to prepare an aqueous phase. Heated. Next, 80 g of [Prepolymer A of crystalline resin] heated to 55 ° C. and put into a flowable state was added to the aqueous phase, and stirred for 10 minutes at 8000 rpm using an Ultra Turrax T50 manufactured by IKA. Then, it was removed until the ethyl acetate concentration reached 0.5% by mass to prepare a crystalline resin latex 2 having a center diameter of 350 nm. The solid content concentration of the latex was 10% by mass.

(Preparation of cyan pigment dispersion B-1)
The materials having the following composition were mixed and dissolved, and dispersed by ultrasonic irradiation with a homogenizer (manufactured by IKA: Ultra Tarrax) to obtain a cyan pigment dispersion B-1 having a central particle size of 150 nm.
Cyan pigment C.I. I. Pigment Blue 15: 3 50g
(Copper phthalocyanine Dainippon Ink Co., Ltd.)
・ Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) 5g
・ Ion exchange water 200g

(Preparation of release agent dispersion C-1)
After mixing the material of the following composition and heating to 97 degreeC, it disperse | distributed by IKA company ultra turrax T50. Then, the dispersion process was carried out with a Gorin homogenizer (manufactured by Reiwa Shoji Co., Ltd.), and 20 times under the conditions of 105 ° C. and 550 kg / cm ² to obtain a release agent dispersion C-1 having a center diameter of 190 nm.
・ [Synthetic ester wax 1] 100 g
・ Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) 5g
・ Ion exchange water 300g

(Preparation of resin particles 11)
-Crystalline resin latex 1 260 parts-Crystalline resin latex 2 120 parts-Cyan pigment dispersion B-1 10 parts-Release agent dispersion C-1 8 parts-Polyaluminum chloride 0.15 parts-Ion-exchanged water 400 Part

After thoroughly mixing and dispersing the above materials in a round stainless steel flask using a homogenizer (IKA, Ultra Turrax T50), the flask was heated to 48 ° C. with stirring in an oil bath for heating. Aggregation was performed. When it was confirmed that the particle size became 5.7 μm, the pH in the system was adjusted to 6.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and the mixture was heated to 70 ° C. while stirring was continued. While the temperature was raised to 70 ° C., the pH in the system dropped to about 5.6, but was maintained as it was. When the circularity reached 0.972, it was cooled.
Then, after filtration, 300 parts of ion-exchanged water was added to the obtained filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, the operation of filtering was performed twice.
Next, 300 parts of ion-exchanged water is added to the obtained filter cake, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered three times. 300 parts of 1% by mass hydrochloric acid was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. Finally, 300 parts of ion-exchanged water was added to the obtained filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, the operation of filtering was performed twice to obtain a filter cake.
The obtained cake was crushed and then dried at 40 ° C. for 22 hours to obtain [Resin Particles 11] having a volume average particle size of 5.6 μm.

(Preparation of Toner 11)
100 parts of the obtained [resin particles 11] and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were used at a peripheral speed of 30 m / sec using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After 5 cycles of mixing for 30 seconds and resting for 1 minute, toner 11 was prepared by sieving with a mesh having an opening of 35 μm.

[Example 12]
[Resin particles 12] were obtained in the same manner as in Example 1 except that the colorant dispersion 1 was not used, and a toner 12 was produced using this.

[Example 13]
[Resin particle 13] is obtained in the same manner as in Example 5 except that the number of parts of [Releasing Agent Dispersion Liquid 8] in Example 5 is changed from 14 parts to 77 parts, and this is used to obtain Toner 13. Produced. The content of the release agent in the toner 13 was 22% by mass.

[Example 14]
[Resin particles 14] were obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] in Example 1 was changed to [Releasing agent dispersion 10]. Produced. The toner 14 was blocked after being left at 50 ° C. for a day, but this did not occur with the toners 1 to 13.

[Example 15]
[Resin particle 15] was obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] in Example 1 was changed to [Releasing agent dispersion 11], and this was used to obtain toner 15. Produced. The toner 15 blocked when left at 50 ° C. for one day.

[Example 16]
[Resin Solution 3] 25 parts, [Amorphous Resin 1] 10 parts, Ethyl Acetate 10 parts, [Resin Solution 6] 10 parts, [Amorphous Prepolymer B] 5 parts, [Releasing Agent] 14 parts of Dispersion 1 and 10 parts of Colorant Dispersion 1 are added, stirred at 8,000 rpm with a TK homomixer at 50 ° C., and uniformly dissolved and dispersed to obtain [Toner Material Liquid 16]. It was.
[Resin particles 16] were obtained in the same manner as in Example 1 except that [Toner material liquid 6] in Example 1 was changed to [Toner material liquid 16]. Toner 16 was produced using this.

[Example 17]
[Resin particle 17] was obtained in the same manner as in Example 1 except that 0.06 part of [nucleating agent] (ADEKA STAB NA-11, melting point 400 ° C., manufactured by ADEKA) was added to the toner material liquid. A toner 17 was prepared using

[Example 18]
[Resin particle 18] was obtained in the same manner as in Example 1 except that [Resin solution 6] in Example 1 was changed to [Amorphous prepolymer B], and toner 18 was produced using this. .

[Comparative Example 1]
[Resin particle 101] was obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] was changed to [Releasing agent dispersion 3], and toner 101 was produced using this.

[Comparative Example 2]
[Resin particle 102] was obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] was changed to [Releasing agent dispersion 9], and toner 102 was produced using this.

[Comparative Example 3]
[Resin particle 103] was obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] was changed to [Releasing agent dispersion 6], and toner 103 was produced using this.

[Comparative Example 4]
[Resin particle 104] was obtained in the same manner as in Example 1 except that [Releasing agent dispersion 1] was changed to [Releasing agent dispersion 7], and toner 104 was produced using this.

  For the toners of the above examples and comparative examples, (C) / [(C) + (A)], T1-T2, T2, the proportion of resins having a molecular weight of 100,000 or more, the weight average molecular weight, ΔH (H) / ΔH (T) was measured. In addition, fixing releasability, low-temperature fixing property, and fixing paper discharge port contamination were evaluated as follows. The results are summarized in Table 1.

[Fixing releasability]
As shown in FIG. 3, a solid image having a width of 50 mm and a toner adhesion amount of 0.85 ± 0. Ten sheets were formed at 1 mg / cm ² . A fixing belt of an electrophotographic copying machine (MF-200, manufactured by Ricoh) using a Teflon (registered trademark) roller is used as a fixing roller. The state of paper release when an image produced at 220 ° C. was passed was evaluated according to the following criteria.

A: All 10 sheets could be fixed without problems.
○ …… Some sheets were caught in the fixing roller, but there was no paper jam.
Δ: One or two paper jammed around the fixing roller.
▲ …… There were 3-6 paper jammed around the fixing roller.
×: 7 or more sheets were caught in the fixing roller and jammed.

Further, when an image surface that passed through the paper without problems was set at 160 ° C., the presence or absence of image scratches (conveying scratches) in the paper passing direction was confirmed and evaluated according to the following criteria.

◎ …… No flaws are seen in the conveyance.
○ …… Transfer scratches are slightly seen depending on the viewing angle.
Δ: Slightly scratched transport can be confirmed from any angle.
× …… Conveyed scratches can be clearly seen from any angle.

[Low temperature fixability]
Using the same apparatus as in the case of [Fixing releasability], the temperature of the fixing belt is increased from 85 ° C. to 5 ° C. by external control, and the transfer paper type 6200 (made by Ricoh Co., Ltd.) for plain paper and cardboard is used. A solid fixed image having a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was formed.
Regarding the fixed image, the solid image was visually fixed without any defects, and the drawing tester AD-401 manufactured by Ueshima Seisakusho was used. The sapphire needle tip was run under the condition of contact under the conditions described above. The running surface of the sapphire needle tip was visually observed, and the lowest temperature at which no scratches were seen was defined as the lowest fixing temperature.

[Fixed paper discharge outlet contamination]
[Carrier A] 14 parts of the toner prepared above with respect to 200 parts are used for 3 minutes at 48 rpm using a type of tumbler mixer (made by Willy et Bacofen (WAB)) in which the container rolls and stirs. Uniform mixing was performed to obtain a developer for two-component development. The obtained two-component developer is set in a developing unit of an electrophotographic multifunction machine (MP C4001A SP, manufactured by Ricoh Co., Ltd.), and further, the same toner as that used for the developer is filled in a toner bottle and set. The state of the 1000th image when 1000 continuous solid images were continuously printed was observed and evaluated according to the following criteria.

◎ …… No flaws are seen on the fixed image, and no deposits are found on the fixing discharge port.
○ …… No flaws are seen in the fixed image, but some deposits are seen in the fixing paper discharge port.
Δ: Slight scratches are observed on the fixed image, and deposits are also observed on the fixing discharge port.
×: Clear flaws are observed in the fixed image, and deposits are also observed in the fixing paper discharge port.

Japanese Patent Publication No. 4-24702 Japanese Patent Publication No. 4-24703 JP 2010-77419 A

Claims (15)

  In the toner containing at least a binder resin and a release agent, and the main component of the binder resin is a resin having a crystalline polyester unit, the content of the linear monoester having 48 or more carbon atoms in the release agent is A toner, which is 40% by mass or more.   The toner according to claim 1, wherein the release agent has a melting point of 80 ° C. or less.   The toner according to claim 1, wherein an endothermic peak half width of the release agent is 10 ° C. or less.   The toner according to claim 1, wherein the content of the release agent is 3 to 20% by mass.   In the diffraction spectrum obtained by the X-ray diffractometer of the toner, when the integrated intensity of the spectrum derived from the crystal structure of the binder resin is (C) and the integrated intensity of the spectrum derived from the amorphous structure is (A) The toner according to claim 1, wherein the ratio (C) / [(C) + (A)] is 0.15 or more. The maximum endothermic peak T1 at the second temperature increase in the range of 0 to 150 ° C. in the DSC of the toner and the maximum exothermic peak T2 at the time of temperature decrease satisfy the following relational expression (1): The toner according to any one of the above.
T1-T2 ≦ 30 ° C. and T2 ≧ 30 ° C. (1)
(However, the rate of temperature increase from 0 ° C. to 100 ° C. at the time of temperature increase is 10 ° C./min, and the rate of temperature decrease from 100 ° C. to 0 ° C. is 10 ° C./min.)   A ratio of a molecular weight of 100,000 or more in a gel diffusion chromatography (GPC) measurement of tetrahydrofuran (THF) soluble content of the toner is 5% by mass or more, and a weight average molecular weight (Mw) is 20,000 to 70, The toner according to claim 1, wherein the toner is 000.   The differential scanning calorimeter of the toner in the differential scanning calorimeter (DSC) is ΔH (T) (J / g), and the toner has a differential scanning calorimeter insoluble in the THF / ethyl acetate mixed solvent (weight ratio 50/50). The heat absorption amount in (DSC) is ΔH (H) (J / g), and ΔH (H) / ΔH (T) is 0.2 to 1.25. The toner according to any one of the above.   The toner according to claim 1, wherein the resin having a crystalline polyester unit has either a urethane bond or a urea bond.   The toner according to claim 1, wherein the resin having the crystalline polyester unit is a block polymer of polyester and polyurethane.   The toner according to claim 1, comprising two or more kinds of resins having the crystalline polyester unit.   The toner according to claim 1, wherein the toner is obtained by granulation in an aqueous medium.   Among the above resins, at least one is a modified crystalline resin having an isocyanate group at the terminal, and when the toner particles are granulated by dispersing or emulsifying in an aqueous medium, the resin is elongated or reacted by a reaction with an active hydrogen group. The toner according to claim 1, wherein a binder resin is formed by a crosslinking reaction.   A developer comprising the toner according to claim 1 and a carrier.   An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the static Developing means for developing an electrostatic latent image with toner to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; An image forming apparatus having at least the toner, wherein the toner is the toner according to claim 1.

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